JPWO2018003058A1 - Method for producing cured product, cured product and spectacle lens substrate - Google Patents

Abstract

A curable composition preparation step for preparing a curable composition by mixing a polyiso (thio) cyanate compound with a polythiol compound having a moisture content of less than 20 ppm by mass, and curing the curable composition to obtain a cured product. And a cured product obtained by curing a curable composition comprising a polyiso (thio) cyanate compound and a polythiol compound having a mass-based water content of less than 20 ppm, and a spectacle lens comprising the cured product. A substrate is provided.

Description

  The present invention relates to a method for producing a cured product, a cured product, and a spectacle lens substrate, and more specifically, a method for producing a cured product obtained by curing a curable composition containing a polythiol compound and a polyiso (thio) cyanate compound, and a cured product. And a spectacle lens substrate.

A polythiourethane resin obtained by curing a polythiol compound and a polyiso (thio) cyanate compound is widely used as a material for various optical members such as spectacle lenses (see, for example, Patent Document 1).
Japanese Patent No. 5026432

  One of the physical properties required for the polythiourethane resin is high heat resistance. This is due to the following reason. For example, a spectacle lens is usually shipped as a product lens after one or more functional films (eg, hard coat, antireflection film, etc.) are formed on a lens substrate. The functional film is formed by various film forming methods such as vacuum deposition, coating method in which a coating process including heating is applied after applying a coating solution containing a curable compound, but many film forming methods involve heat treatment. . If the lens substrate is inferior in heat resistance, the quality of the product lens may be deteriorated due to deformation and / or alteration of the lens substrate due to heat treatment. For example, when the lens base material is deformed, the functional film formed on the lens base material may not follow the deformation of the lens base material, and the functional film may crack. On the other hand, if an attempt is made to perform a heat treatment at a heating temperature that the lens substrate can withstand in order to prevent such deterioration of the product lens, the film forming conditions are restricted, and usable film forming materials are also limited. Also, in the manufacturing process of various optical members, not limited to spectacle lenses, it is widely used to subject a resin base material to a process involving heating such as a functional film forming process. In order to provide a new polythiourethane resin, it is desired to improve the heat resistance of the polythiourethane resin.

  One embodiment of the present invention provides means for improving the heat resistance of a polythiourethane resin obtained by curing a polythiol compound and a polyiso (thio) cyanate compound.

One embodiment of the present invention provides:
Curable composition preparation step of preparing a curable composition by mixing a polyiso (thio) cyanate compound with a polythiol compound having a moisture content on a mass basis (hereinafter simply referred to as “moisture content”) of less than 20 ppm. When,
A curing step of curing the curable composition to obtain a cured product;
A method for producing a cured product comprising
About.

  The present inventors are intensively studying to find a means for improving the heat resistance of a cured product (polythiourethane resin) obtained by curing a polythiol compound and a polyiso (thio) cyanate compound. Thus, new knowledge that has not been known so far has been obtained that the moisture contained in the polythiol compound affects the heat resistance of a cured product obtained by curing the polyiso (thio) cyanate compound with the polythiol compound. As a result of further earnest studies based on this finding, the method for producing a cured product according to one embodiment of the present invention was completed.

  According to one embodiment of the present invention, the heat resistance of a cured product obtained by curing reaction of a polythiol compound and a polyiso (thio) cyanate compound can be improved.

One aspect of the present invention relates to a method for producing the cured product.
Furthermore, according to one aspect of the present invention, a cured product obtained by curing a curable composition comprising a polyiso (thio) cyanate compound and a polythiol compound having a moisture content of less than 20 ppm by mass, and a spectacle lens substrate comprising the cured product. Is also provided.
Below, the manufacturing method of the said hardened | cured material, hardened | cured material, and a spectacles lens base material are demonstrated in detail.

を有する反応生成物を得ることができる。上記において、Ｚは酸素原子または硫黄原子である。チオール基がイソシアネート基と反応することによりＺが酸素原子の上記結合が形成され、イソチオシアネート基と反応することによりＺが硫黄原子の上記結合が形成される。本発明および本明細書では、上記結合を１分子中に複数含む反応生成物（樹脂）を、「ポリチオウレタン系樹脂」と記載する。<Curable composition preparation process>
The curable composition contains at least a polythiol compound and a polyiso (thio) cyanate compound. The “polythiol compound” is a polyfunctional compound having two or more thiol groups (—SH) in one molecule. Further, in the present invention and the present specification, the “polyiso (thio) cyanate compound” is used to include a polyisocyanate compound and a polyisothiocyanate compound. It should be noted that isocyanate is sometimes referred to as isocyanate, and isothiocyanate is sometimes referred to as isothiocyanate. The term “iso (thio) cyanate group” is used to include an isocyanate group (—N═C═O) and an isothiocyanate group (—N═C═S). The “polyiso (thio) cyanate compound” is a polyfunctional compound having two or more iso (thio) cyanate groups in one molecule. By curing the polythiol compound and the polyiso (thio) cyanate compound, the thiol group possessed by the polythiol compound reacts with the iso (thio) cyanate group possessed by the polyiso (thio) cyanate compound, resulting in the following bonds in the molecule: :

A reaction product having can be obtained. In the above, Z is an oxygen atom or a sulfur atom. When the thiol group reacts with the isocyanate group, Z forms the above bond of oxygen atom, and when it reacts with the isothiocyanate group, Z forms the above bond of sulfur atom. In the present invention and the present specification, a reaction product (resin) containing a plurality of the bonds in one molecule is referred to as “polythiourethane resin”.

For example, in Patent Document 1 (Japanese Patent No. 5026432), a polymerizable composition comprising a polythiol compound and a polyiso (thio) cyanate compound (described in Patent Document 1 as “polyiso (thio) cyanate compound”). In the method for producing a resin for optical materials that polymerizes the water, it is essential that the water content of the polythiol compound before polymerization is 20 to 600 ppm (see claim 1 of Patent Document 1). Patent Document 1 does not describe any relation between the water content of the polythiol compound and the heat resistance of the polythiourethane resin.
On the other hand, as a result of intensive studies, the present inventors have obtained a new knowledge that has not been known so far that the water content of the polythiol compound affects the heat resistance of the polythiourethane resin. And as a result of further earnest examination based on such knowledge, the moisture content is 20 ppm or more by using a polythiol compound having a moisture content different from the range that is essential in Patent Document 1 in which the moisture content is less than 20 ppm. The present inventors have newly found that a polythiourethane resin having improved heat resistance can be obtained as compared with a polythiourethane resin obtained using the above polythiol compound as a synthesis raw material. The water content of the polythiol compound used in the method for producing a cured product is less than 20 ppm, and from the viewpoint of further improving the heat resistance of the polythiourethane resin, it is preferably 19 ppm or less, and 18 ppm or less. Is more preferably 15 ppm or less, still more preferably 12 ppm or less, and even more preferably 10 ppm or less. The water content of the polythiol compound can be, for example, 5 ppm or more or 7 ppm or more. However, since it is preferable that it is low for improving the heat resistance of the polythiourethane resin, the lower limit exemplified above may be used.

The water content of the polythiol compound in the present invention and in the present specification is a measurement performed by a Karl Fischer method using a water vaporizer in an environment of a temperature of 20 to 25 ° C. and an absolute humidity of 0.8 to 1.2 g / m ^3. Is a value obtained by. The moisture content measurement by the Karl Fischer method may be performed by a coulometric titration method or a volumetric titration method.

  As a method for reducing the water content of the polythiol compound, one or a combination of two or more methods such as a nitrogen bubbling method, a vacuum degassing method, an adsorption method in which anhydrous sodium sulfate or molecular sieve is immersed can be used. Thereby, a polythiol compound having a water content of less than 20 ppm can be obtained.

  As a polythiol compound, various polythiol compounds, such as an aliphatic polythiol compound and an aromatic polythiol compound, can be used. The number of thiol groups contained in one molecule of the polythiol compound is 2 or more, preferably 2 to 6, and more preferably 2 to 4. Specific examples of the polythiol compound include various polythiol compounds exemplified in paragraphs 0035 to 0044 of WO2008 / 047626A1. Preferred polythiol compounds include bis (mercaptomethyl) -3,6,9, -trithia-undecanedithiol, 2,3-bismercaptoethylthio-1-mercaptopropane, bismercaptomethyldithiane, pentaerythritol tetrakismercaptoacetate, Mention may be made of pentaerythritol tetrakismercaptopropionate, trimethylolpropane trismercaptoacetate, trimethylolpropane trismercaptopropionate. These compounds may be used alone or in combination of two or more.

  Examples of the polyiso (thio) cyanate compound mixed with the polythiol compound for preparing the curable composition include aliphatic polyiso (thio) cyanate compounds, alicyclic polyiso (thio) cyanate compounds, and aromatic polyiso (thio). Various polyiso (thio) cyanate compounds such as cyanate compounds can be used. The number of iso (thio) cyanate groups contained in one molecule of the polyiso (thio) cyanate compound is 2 or more, preferably 2 to 4, and more preferably 2 or 3. Specific examples of the polyiso (thio) cyanate compound include various compounds exemplified as a polyiso (thio) cyanate compound in Japanese Patent No. 5319037, paragraph 0052. Preferred polyiso (thio) cyanate compounds include hexamethylene diisocyanate, 1,5-pentane diisocyanate, isophorone diisocyanate, bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane diisocyanate, 2,5-bis (isocyanatomethyl) -bicyclo [2 2.1] heptane, 2,6-bis (isocyanatomethyl) -bicyclo [2.2.1] heptane, bis (4-isocyanatocyclohexyl) methane, 1,3-bis (isocyanatomethyl) Aliphatic polyisocyanate compounds such as cyclohexane and 1,4-bis (isocyanatomethyl) cyclohexane; bis (isocyanatomethyl) benzene, m-xylylene diisocyanate, p-xylylene diisocyanate, 1,3-diisocyanatobenzene And aromatic polyisocyanate compounds such as tolylene diisocyanate, 2,4-diisocyanatotoluene, 2,6-diisocyanatotoluene, and 4,4′-methylenebis (phenylisocyanate). Furthermore, halogen substituted products such as chlorine-substituted products and bromine-substituted products of the above polyiso (thio) cyanate compounds, alkyl-substituted products, alkoxy-substituted products, nitro-substituted products and prepolymer-modified products with polyhydric alcohols, carbodiimide-modified products, Urea-modified products, burette-modified products, dimerization or trimerization reaction products, and the like can also be used. These compounds may be used alone or in combination of two or more.

  The curable composition can be prepared by mixing a polyiso (thio) cyanate compound with a polythiol compound having a water content of less than 20 ppm. The mixing ratio of the polythiol compound and the polyiso (thio) cyanate compound in the curable composition is not particularly limited. For example, as a molar ratio, the thiol group contained in the polythiol compound / the isoform contained in the polyiso (thio) cyanate compound. The (thio) cyanate group = 0.5 to 3.0, preferably 0.8 to 1.4, and more preferably 0.9 to 1.1. Setting the mixing ratio in the above range is preferable for obtaining a curable composition capable of providing a cured product having various excellent physical properties such as a high refractive index and high heat resistance.

  At the time of preparing the curable composition, one or more other components other than the polyiso (thio) cyanate compound and the polythiol compound having a water content of less than 20 ppm may be mixed. Specific examples of such other components include a reaction catalyst for a curing reaction between a polythiol compound and a polyiso (thio) cyanate compound. For other components that may be mixed, reference can be made to, for example, Japanese Patent No. 5319037, paragraphs 0055, 0057, and 0058-0064. In addition, one or more kinds of additives generally available as additives for various resins such as polythiourethane resins can be used. Preparation of the said curable composition can be performed by mixing the various components demonstrated above simultaneously or sequentially in arbitrary orders. The preparation method is not particularly limited, and any known method for preparing a curable composition can be employed without any limitation.

<Curing process>
By curing the curable composition prepared in the curable composition preparation step described above, a polythiourethane resin useful as a material for optical members such as eyeglass lenses can be obtained as a cured product. By using a polythiol compound having a water content of less than 20 ppm as the polythiol compound, it is possible to obtain a cured product (polythiourethane resin) having high heat resistance compared to the case of using a polythiol compound having a water content of 20 ppm or more. Become. A glass transition temperature (Tg) can be mentioned as an index of heat resistance. The glass transition temperature (Tg) in this invention and this specification means the glass transition temperature measured by the thermomechanical analysis (TMA) penetration method based on JISK7196-2012. For specific measurement methods, the examples described later can be referred to. Regarding the heat resistance using the glass transition temperature (Tg) as an index, for example, improvement of 2 ° C. or more as Tg, for example, improvement of about 2 to 10 ° C. is in the field of manufacturing various optical members including the field of eyeglass lenses. It is preferable for increasing the usefulness of the polythiourethane resin. The improvement in heat resistance of the polythiourethane resin by using a polythiol compound having a water content of less than 20 ppm as the polythiol compound is more preferably 3 ° C. or more, and further preferably 4 ° C. or more, as the glass transition temperature (Tg). Yes, more preferably 5 ° C or higher.

  The curing reaction between the polyiso (thio) cyanate compound and the polythiol compound having a water content of less than 20 ppm can be performed by various curing treatments capable of curing the curable composition. For example, cast polymerization is preferable for producing a cured product having a lens shape (also referred to as “plastic lens”). In casting polymerization, a curable composition is injected into a cavity of a mold having two molds facing each other with a predetermined interval and a cavity formed by closing the interval, and the curable composition is injected into the cavity. A cured product can be obtained by polymerization (curing reaction). For details of the mold that can be used for cast polymerization, reference can be made, for example, to paragraphs 0012 to 0014 of JP-A-2009-262480 and FIG. In the above publication, a mold in which the interval between two molds is closed with a gasket as a sealing member is shown, but a tape may be used as the sealing member.

  In one aspect, cast polymerization can be performed as follows. The curable composition is injected into the mold cavity from the injection port provided on the side surface of the mold (injection process). After the injection, the curable composition is preferably polymerized (curing reaction) by heating, so that the curable composition is cured and a cured product to which the internal shape of the cavity is transferred can be obtained (curing step). The polymerization conditions are not particularly limited, and can be appropriately set according to the composition of the curable composition. As an example, a mold in which a curable composition is injected into a cavity can be heated at a heating temperature of 20 to 150 ° C. for about 1 to 72 hours, but is not limited to this condition. In the present invention and the present specification, the temperature such as the heating temperature related to the casting polymerization refers to an atmospheric temperature at which the mold is disposed. Further, during heating, the temperature can be increased at an arbitrary temperature increase rate, and the temperature can be decreased (cooled) at an arbitrary temperature decrease rate. After the polymerization (curing reaction) is completed, the cured product inside the cavity is released from the mold. As is usually done in casting polymerization, the cured product can be released from the mold by removing the upper and lower molds forming the cavity and the gasket or tape in any order. The cured product released from the mold can be preferably used as a lens base material for spectacle lenses. In addition, the cured product used as the lens base material of the spectacle lens is usually a primer coating layer for improving impact resistance, an annealing process, a grinding process such as a rounding process, a primer coating layer for improving the surface hardness after release. It can attach | subject to post processes, such as coat layer formation processes, such as a hard-coat layer. Furthermore, various functional layers such as an antireflection layer and a water repellent layer can be formed on the lens substrate. For these steps, any known technique can be applied without any limitation. Thus, a spectacle lens whose lens base material is the cured product can be obtained. Furthermore, spectacles can be obtained by attaching this spectacle lens to a frame.

  EXAMPLES Next, although an Example demonstrates this invention still in detail, this invention is not limited to the aspect shown in an Example. Unless otherwise specified, the operations and evaluations described below were performed at room temperature in the atmosphere (about 20 to 25 ° C.). Further,% and parts described below are based on mass unless otherwise specified.

[Measurement of water content of polythiol compound]
The water content of the polythiol compound used for preparing the curable compositions in Examples and Comparative Examples was measured by Karl Fischer moisture under an environment of a temperature of 20 to 25 ° C. and an absolute humidity of 0.8 to 1.2 g / m ^3. It measured using the apparatus (Kyoto Electronics Industry Co., Ltd. automatic moisture measuring device MKC-610 type | mold) and the moisture vaporizer (Kyoto Electronics Industry Co., Ltd. moisture vaporizer ADP-611 type | mold).
The polythiol compound used in the examples is a polythiol compound obtained by reducing the water content by degassing a commercially available thiol compound (60 ° C., 100 Pa). The water content was adjusted by the time during which vacuum degassing was performed. For example, in Example 1, vacuum degassing was performed for 2 hours.
A curable composition was prepared within 1 hour after the measurement of the water content. Even if the water content of the polythiol compound does not change or changes between the measurement of the water content and the preparation of the curable composition, the amount of change is below the detection limit. Further, in a normal working environment or storage environment, even if the water content of the polythiol compound does not change or changes, the amount of change is below the detection limit.

[Measurement of glass transition temperature (Tg) of cured product (plastic lens made of polythiourethane resin)]
The glass transition temperature (Tg) of the cured product obtained in Examples and Comparative Examples was measured by a penetration method using a thermal instrument analyzer TMA8310 manufactured by Rigaku Corporation. The heating rate during measurement was 10 K / min, and an indenter having a diameter of 0.5 mm was used as an indenter for the penetration method.

[Example 1]
(Curable composition preparation process)
50.6 parts of xylylene diisocyanate, 0.01 parts of dimethyltin dichloride as a curing catalyst, 0.20 parts of acidic phosphate ester (JP-506H, manufactured by Johoku Chemical Industry Co., Ltd.), UV absorber (Cipro Kasei) SEASORB 701) 0.50 part was mixed and dissolved. Furthermore, 49.4 parts of bis (mercaptomethyl) -3,6,9-trithia-undecanedithiol having a water content shown in Table 1 were added and mixed to obtain a mixed solution. The mixture was degassed at 200 Pa for 1 hour, and then filtered through a PTFE (polytetrafluoroethylene) filter having a pore size of 5.0 μm.

(Injection process)
The filtered mixed solution (curable composition) was poured into a lens mold composed of a glass mold having a diameter of 75 mm and −4.00 D and a tape.

(Curing process, annealing)
The mold was put into an electric furnace, gradually heated from 15 ° C. to 120 ° C. over 20 hours, and held for 2 hours for polymerization (curing reaction). After completion of the polymerization, the mold was taken out from the electric furnace and released to obtain a cured product (plastic lens made of polythiourethane resin). The obtained plastic lens was further annealed in an annealing furnace at a furnace temperature of 120 ° C. for 3 hours.

  Said curable composition preparation process and injection | pouring process were performed in the atmosphere which controlled absolute humidity to the value shown in Table 1.

[Example 2]
A cured product was obtained in the same manner as in Example 1 except that the curable composition preparation step and the injection step were performed in an atmosphere in which the absolute humidity was controlled to the value shown in Table 1.

[Example 3]
A cured product was obtained in the same manner as in Example 1 except that bis (mercaptomethyl) -3,6,9-trithia-undecanedithiol having a moisture content shown in Table 1 was used.

[Example 4]
A cured product was obtained in the same manner as in Example 3 except that the curable composition preparation step and the injection step were performed in an atmosphere in which the absolute humidity was controlled to the value shown in Table 1.

[Comparative Example 1 and Comparative Example 2]
A cured product was obtained in the same manner as in Example 1 except that bis (mercaptomethyl) -3,6,9-trithia-undecanedithiol having a moisture content shown in Table 1 was used.

[Comparative Example 3]
A cured product was obtained in the same manner as in Comparative Example 2, except that the curable composition preparation step and the injection step were performed in an atmosphere in which the absolute humidity was controlled to the value shown in Table 1.

[Example 5]
50.6 parts of xylylene diisocyanate was changed to 47.6 parts of bisisocyanatomethylcyclohexane, the amount of curing catalyst (dimethyltin dichloride) was changed to 0.40 parts, and bis (mercaptomethyl)- Example 1 except that 3,6,9-trithia-undecanedithiol was changed to a mixture of 26.2 parts bismercaptomethyldithiane and 26.2 parts pentaerythritol tetrakismercaptoacetate (water content: see Table 1). Similarly, a cured product was obtained.

[Example 6]
Using a mixture of 26.2 parts of bismercaptomethyldithiane and 26.2 parts of pentaerythritol tetrakismercaptoacetate (moisture content: see Table 1), the curable composition preparation step and the injection step are expressed in terms of absolute humidity. A cured product was obtained in the same manner as in Example 5 except that it was performed in an atmosphere controlled to the value shown in 1.

[Comparative Example 4]
A cured product was obtained in the same manner as in Example 5, except that a mixture of 26.2 parts of bismercaptomethyldithiane and 26.2 parts of pentaerythritol tetrakismercaptoacetate (water content: see Table 1) was used.

[Example 7]
50.6 parts of xylylene diisocyanate was changed to 50.3 parts of bisisocyanatomethylbicycloheptane, the amount of curing catalyst (dimethyltin dichloride) was changed to 0.05 parts, and bis (mercaptomethyl) -3,6 , 9-trithia-undecanedithiol was changed to Example 1 except that 24.2 parts of bismercaptoethylthiomercaptopropane and 25.5 parts of pentaerythritol tetrakismercaptopropionate (water content: see Table 1) were used. Similarly, a cured product was obtained.

[Example 8]
Using a mixture of 24.2 parts of bismercaptoethylthiomercaptopropane and 25.5 parts of pentaerythritol tetrakismercaptopropionate (water content: see Table 1), the curable composition preparation step and the injection step must be A cured product was obtained in the same manner as in Example 7 except that the humidity was controlled in an atmosphere controlled to the value shown in Table 1.

[Comparative Example 5]
A cured product was obtained in the same manner as in Example 7, except that a mixture (water content: see Table 1) of 24.2 parts of bismercaptoethylthiomercaptopropane and 25.5 parts of pentaerythritol tetrakismercaptopropionate was used. .

  The glass transition temperature of the cured product (polythiourethane resin plastic lens) obtained in the above Examples and Comparative Examples was measured by the method described above.

  The results are shown in Table 1. From the comparison between Examples 1-4 and Comparative Examples 1-3, the comparison between Examples 5, 6 and Comparative Example 4, and the comparison between Examples 7, 8 and Comparative Example 5, the polythiol compound having a water content of less than 20 ppm. It can be confirmed that the heat resistance of the cured product (polythiourethane resin plastic lens) is improved (specifically, the glass transition temperature is improved by 3 ° C. or more). In addition, the difference in heat resistance is hardly seen between Example 1 and Example 2 which performed the curable composition preparation process and injection | pouring process in the atmosphere of different absolute humidity using the polythiol compound of the same moisture content. On the other hand, when comparing Examples 1 and 3 and Comparative Examples 1 and 2 in which the curable composition preparation step and the injection step were performed in an atmosphere of the same absolute humidity using polythiol compounds having different moisture contents, In Examples 1 and 3, an improvement in heat resistance (specifically, an improvement of 3 ° C. or more as the glass transition temperature) was achieved with respect to Comparative Examples 1 and 2. From this result, it can be confirmed that the moisture derived from the polythiol compound greatly affects the heat resistance of the polythiourethane resin.

[Evaluation of striae and cloudiness]
The following evaluation was implemented about the hardened | cured material (plastic lens made from a polythiourethane type resin) obtained by the said Example and comparative example. If the evaluation results of striae and white turbidity are both B or more, it can be determined that the cured product is extremely homogeneous and excellent in transparency and suitable as a spectacle lens substrate.

(Evaluation of striae)
About the said plastic lens, the projection test | inspection was performed using the Ushio Electric Co., Ltd. external appearance inspection apparatus Optical Modulex SX-UI251HQ. As a high-pressure ultraviolet (UV) lamp as a light source, USH-102D manufactured by Ushio Electric Co., Ltd. was used, and a white screen was installed at a distance of 1 m from the light source. The plastic lens to be evaluated was inserted between the light source and the screen, and the projected image on the screen was visually observed and judged according to the following criteria.
A ⁺ : A linear defect is not confirmed in the projected image.
A: A very thin linear defect is confirmed in the projected image.
B: A linear thin defect is confirmed in the projected image.
C: A linear dark defect is confirmed in the projected image.
D: A remarkable linear defect is confirmed in the projected image.

(Evaluation of cloudiness)
The plastic lens was visually observed under a fluorescent lamp in a dark box and judged according to the following criteria.
A ⁺ : No cloudiness is confirmed in the plastic lens.
A: A very thin cloudiness is confirmed on the plastic lens.
B: Thin cloudiness is confirmed on the plastic lens.
C: Dark cloudiness is confirmed in the plastic lens.
D: Remarkable white turbidity is confirmed in the plastic lens.

  The results are shown in Table 2. From the results shown in Table 2, it can be confirmed that by using a polythiol compound having a water content of less than 20 ppm, striae of the cured product (plastic lens made of polythiourethane resin) and suppression of white turbidity were also achieved.

  Finally, the above-described aspects are summarized.

  According to one aspect, a curable composition preparation step of preparing a curable composition by mixing a polyiso (thio) cyanate compound with a polythiol compound having a moisture content of less than 20 ppm by mass, and the curable composition described above. The manufacturing method of hardened | cured material including the hardening process which hardens | cures and obtains hardened | cured material can be provided.

  According to the manufacturing method of said hardened | cured material, the hardened | cured material (polythiourethane type | system | group) obtained by the hardening reaction of a polyiso (thio) cyanate compound and a polythiol compound by using the polythiol compound whose water content of mass reference | standard is less than 20 ppm. Resin) can be improved in heat resistance.

  In one aspect, the water content based on mass of the polythiol compound is 5 ppm or more and less than 20 ppm.

In one aspect, the curable composition preparation step comprises an absolute humidity of 18 g / m ³ or less, preferably 15 g / m ³ or less, more preferably 12 g / m ³ or less, still more preferably less than 12 g / m ³ , more preferably It is carried out in an atmosphere of 10 g / m ³ or less, more preferably less than 10 g / m ³ .

  In one aspect, the curing step is performed by subjecting the curable composition to cast polymerization.

In one aspect, the step of injecting the curable composition into a mold for casting polymerization (injection step) has an absolute humidity of 18 g / m ³ or less, preferably 15 g / m ³ or less, more preferably 12 g / m. ³ or less, more preferably less than 12 g / m ³ , more preferably 10 g / m ³ or less, and even more preferably less than 10 g / m ³ .

  In one aspect, the cured product is a spectacle lens substrate.

  According to another aspect, there is provided a cured product obtained by curing a curable composition containing a polyiso (thio) cyanate compound and a polythiol compound having a moisture content of less than 20 ppm by mass.

  The said hardened | cured material can show high heat resistance. In one aspect | mode, the glass transition temperature (Tg) of the said hardened | cured material is 98 degreeC or more, Preferably it is 100 degreeC or more (for example, the range of 100-150 degreeC).

  In one aspect, the water content based on mass of the polythiol compound is 5 ppm or more and less than 20 ppm.

  According to another aspect, a spectacle lens substrate made of the cured product is also provided.

  The embodiment disclosed this time should be considered as illustrative in all points and not restrictive. The scope of the present invention is defined by the terms of the claims, rather than the description above, and is intended to include any modifications within the scope and meaning equivalent to the terms of the claims.

  One embodiment of the present invention is useful in the field of manufacturing various optical members such as eyeglass lenses.

Claims (7)

A curable composition preparation step of preparing a curable composition by mixing a polyiso (thio) cyanate compound with a polythiol compound having a mass-based moisture content of less than 20 ppm;
A curing step of curing the curable composition to obtain a cured product;
The manufacturing method of the hardened | cured material containing this. The manufacturing method of the hardened | cured material of Claim 1 whose moisture content of the mass reference | standard of the said polythiol compound is 5 ppm or more and less than 20 ppm. The manufacturing method of the hardened | cured material of Claim 1 or 2 which performs the said hardening process by attaching | subjecting the said curable composition to cast polymerization. The manufacturing method of the hardened | cured material of any one of Claims 1-3 whose said hardened | cured material is a spectacles lens base material. A cured product obtained by curing a curable composition containing a polyiso (thio) cyanate compound and a polythiol compound having a moisture content on a mass basis of less than 20 ppm. The hardened | cured material of Claim 5 whose moisture content of the mass reference | standard of the said polythiol compound is 5 ppm or more and less than 20 ppm. The spectacle lens base material which consists of hardened | cured material of Claim 5 or 6.